The present invention consists of co-compounded silicone and organic rubbers which are made compatible by the addition of a second organopolysiloxane which contains long chain carbon substituents on silicon.
Various attempts have been made to manufacture rubber products by the vulcanization of blends of unvulcanized natural or synthetic rubber with unvulcanized organopolysiloxane rubber using peroxides as catalysts. The object in compounding natural or synthetic organic rubber with silicone rubber is to take advantage of the physical properties of each rubber in order to enhance the physical properites of the final rubber product. However, in such compounded rubber systems, the differences in polymer solubility coefficients and viscosities is excessively great, and homogeneous dispersion by compounding is difficult. There are also great differences in the rates of vulcanization in the presence of organic peroxides. In addition, the heat co-vulcanization is difficult.
After vulcanization these prior art compounded rubbers have poor heat resistance just as do natural rubber or synthetic rubbers.
The inventor herein compounded rubber from natural rubber or synthetic rubber and silicone rubber, in an effort to obtain rubber compositions capable of being vulcanized with organic peroxides but not having the above-mentioned disadvantages.
When organopolysiloxanes that are substituted with monovalent aliphatic hydrocarbon radicals with 4-20 carbon atoms are added as a third component, the above-mentioned disadvantages of compounded rubbers are overcome.
This invention therefore consists of a composition of matter consisting essentially of (a) 5-95 parts by weight of an unvulcanized rubber selected from the group consisting of (i) natural rubber and (ii) synthetic organic rubber; (b) 5-95 parts by weight of an unvulcanized organopolysiloxane rubber wherein the silicon atoms in the organopolysiloxane rubber are attached to monovalent hydrocarbon radicals or substituted monovalent hydrocarbon radicals selected from a group consisting of methyl, vinyl, phenyl and 3,3,3-trifluoropropyl radicals and wherein at least 50 mol percent of all the hydrocarbon radicals are methyl; (c) 1-30 parts by weight based on 100 parts by weight of components (a) and (b) of an organopolysiloxane having the average unit formula ##EQU1## wherein R is a substituted or unsubstituted monovalent hydrocarbon radical selected from the group consisting of methyl, ethyl, vinyl, phenyl, naphthyl, .beta.-phenylethyl, 2-phenylpropyl, 3-chloropropyl and 3,3,3-trifluoropropyl radicals and R' is a substituted or unsubstituted aliphatic monovalent hydrocarbon radical of 4 to 20 carbon atoms, a has a value of 1 to 2.5 and b has a value of 0.01 to 1.2 and a+b has a value of 1.9 to 3; (d) 0.1-15 parts by weight based on 100 parts by weight of components (a) and (b) of an organic peroxide.
Component (a), the organic rubbers, can be those types of rubbers which can be vulcanized in the presence of organic peroxides. These rubbers include natural raw rubber and synthetic rubber. Examples of synthetic rubber useful in this invention are isoprene polymers, butadiene polymers, styrene/butadiene copolymers, isoprene/isobutylene copolymers, chloroprene polymers, butadiene/acrylonitrile copolymers, ethylene/propylene copolymers, ethylene/propylene terpolymers, vinyl compound/acrylate copolymers (Acryl), polyester/isocyanate condensation products, polyester/isocyanate condensation products (polyurethanes), polyethers, ethylene/vinyl acetate copolymers, and chlorosulfonated polyethylenes. Ethylene/propylene terpolymers used in the present invention are terpolymers of ethylene, propylene and diene or triene.
Unvulcanized rubber with a high degree of crystallinity can be used directly. The conventional additives generally added to natural and synthetic rubbers such as reinforcing fillers, bulking agents, vulcanization auxiliaries, plasticizers, softening agents, pigments, antioxidants, and flame retardancy agents, can be added to the unvulcanized rubber. The types and the amounts of such additives can be appropriately selected according to the type of unvulcanized rubber used. However, the above expression "100 parts by weight" should be understood to mean "100 parts by weight of polymer".
These rubbers can be used singly or in combinations of two or more rubbers. The amount of component (a) employed depends upon the intended use of the product. It varies with the characteristics which are either based on the component (a) or component (b). The amount generally ranges from 5 to 95 parts by weight relative to 100 parts by weight of components (a) and (b) added together (calculated as polymer component without adjuvants).
Component (b), the diorganopolysiloxane rubber, in the present invention, is primarily a straight-chain diorganopolysiloxane with a high degree of polymerization having the unit formula ##EQU2## where R" is methyl, vinyl, phenyl or 3,3,3-trifluoropropyl radicals with methyl radicals constituting at least 50 mol % of all the organic radicals, and c is a number from 1.98 to 2.05.
Substances of the above type must be in the form of unvulcanized rubber. No restriction is placed on the degree of polymerization. It generally ranges from 1000 to about 10,000. Examples of units constituting the diorganopolysiloxane useful in this invention are dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, methylvinylsiloxane, phenylvinylsiloxane, and methyl-3,3,3-trifluoropropylsiloxane.
The diorganopolysiloxane can be a homopolymer or copolymers of these units, or a mixture of these polymers. However, methyl groups constitute at least 50 mol % of all the organic radicals. Units of the formula R"'SiO.sub.1.5, where R'" has the meaning set forth above, for R" can be included in the structure in small amounts. The molecular chain end groups can be hydroxyl, alkoxy, trimethylsilyl, dimethylphenylsilyl and methylphenylvinylsilyl groups. The diorganopolysiloxane rubber component (b) can be compounded directly with components (a) and (c). However, reinforcing fillers such as fumed silica or wet process silica, and other additives which are commonly added to silicon rubbers can be added prior to compounding with other components.
Generally, from 5-95 parts by weight of component (b) is used in this invention.
Component (c), the organopolysiloxane, is an indispensable component in order to form a satisfactorily and homogeneously dispersed blend by improving the compatibility between the unvulcanized natural rubber or synthetic rubber and the organopolysiloxane unvulcanized rubber or silicone rubber, in order to be able to carry out the co-vulcanization in the presence of organic peroxides, and in order to improve the heat resistance of the vulcanized rubber product.
Component (c) is an organopolysiloxane having the average unit formula ##EQU3## wherein R is a substituted or unsubstituted monovalent hydrocarbon radical selected from the group consisting of methyl, vinyl, phenyl and 3,3,3-trifluoropropyl radicals and R' is a substituted or unsubstituted aliphatic monovalent hydrocarbon radical of 4-20 carbon atoms, a has a value of 1 to 2.5 and b has a value of 0.01 to 1.2 and a+b has a value of 1.9 to 3.
Examples of R useful in this invention are methyl, ethyl, propyl, vinyl, phenyl, naphthyl, .beta.-phenylethyl, 2-phenylpropyl, 3-chloropropyl, and 3,3,3-trifluoropropyl radicals. Examples of R' useful in this invention are n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, 3-methylpentyl, cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, 3,3-dimethylpentyl, n-nonyl, n-decyl, n-dodecyl, stearyl, palmityl and oleyl groups, and those in which one or more hydrogen atoms of long chain alkyl groups are replaced with chlorine atoms, hydroxyl groups or phenyl groups. However, unsubstituted aliphatic hydrocarbon and aralkyl radicals are the most useful.
a is a number of from 1 to 2.5, b is a number from 0.01 to 1.2, and a+b is a number from 1.9 to 3. R generally represents methyl, vinyl, phenyl or trifluoropropyl groups. b is preferably a number from 0.1 to 1.2 from the standpoint of improvement in heat resistance of the cured rubbers.
From the standpoint of molecular structure, molecules with a straight-chain structure or with a cyclic structure and with a+b of 2-3 are preferable. However, a slight amount of branched structure or three-dimensional network structure is allowable. The end groups of the molecules of straight-chain structure and slightly branched chain structure can include hydroxyl groups in addition to R and R'.
The degree of polymerization of component (c) is preferably above 2 but the upper limit is not particularly critical. In practice the degree of polymerization should not be more than about ten thousand due to inherent limitations of the available polymerization techniques.
The viscosity at 25.degree. C. should preferably be below 100,000 cSt (100 Pa.sup.. s).
The amount of component (c) useful in this invention ranges from 1 to 30 parts by weight, relative to 100 parts by weight of the sum of components (a) and (b). If the amount is less than 1 part by weight, the improvement in the heat resistance is inadequate, whereas if the amount is greater than 30 parts by weight, the effects on the processability and physical properties of the resulting rubber become too great.
Component (d) in the present invention is an organic peroxide which is conventionally used with unvulcanized natural rubbers and synthetic rubbers. Examples of component (d) useful in this invention are benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexene, 2,5-bis(tert-butylperoxy)-2,5 dimethylhexane, dialkyl peroxide, ketal peroxide and 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane.
The types of organic peroxides used in the present invention can be appropriately selected according to the types of natural rubber and synthetic rubber employed. The amount useful ranges from 0.1 to 15 parts by weight relative to 100 parts by weight of sum of components (a) and (b) (as polymer content).
The composition of the present invention can be obtained by the homogeneous blending of the four components (a), (b), (c) and (d). As mentioned in this specification for component (a), the conventional additives used with natural rubber and synthetic rubber can be optionally added to the compositions. Examples of these additives are as follows: reinforcing fillers and bulking agents: fumed silica, wet process silica, fine quartz powder, diatomaceous earth, carbon black, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium oxide, talc, mica powder, aluminum sulfate, calcium sulfate, barium sulfate, asbestos, glass fiber, organic reinforcing agents, and organic fillers; vulcanization auxiliaries: metal oxides, amines, fatty acids and their derivatives; plasticizers: polydimethylsiloxane oils, phthalic acid derivatives, and adipic acid derivatives; softening agents: lubricating oil, process oil, coal tar, castor oil, beeswax, ricinolic acid, calcium stearate; antioxidants: phenylenediamines, phosphites, quinolines, cresols, phenols, and dithiocarbamate metal salts; and other additives such as colorants, UV absorbers, heat resisting agents, flame retardancy agents, foaming agents, scorch retarders, tackifiers and lubricants.
As mentioned in this specification for component (b), the conventional additives used with silicone rubber can be optionally added to the compositions. Examples of these additives are as follows: reinforcing fillers and bulking fillers: fumed silica, wet process silica, fine quartz powder, diatomaceous earth, carbon black, zinc white, magnesium silicate, aluminum silicate, titanium oxide, talc, mica powder, calcium sulfate, barium sulfate, asbestos, glass fiber; agents conventionally used for treating reinforcing fillers: low molecular weight alkoxy-terminal polydimethylsiloxane, diphenylsilanediol, trimethylsilanol; heat resistant agents such as iron oxides, cerium oxide, iron naphthenate, cerium naphthenate; flame retarders; oil resistance agents; foaming agents; and adhesion additives.
The compounded rubber of this invention can be prepared in the following manner. Component (a) is softened by blending using a Banbury mixer, kneader or a two-roll mill. Components (b) and (c) are added simultaneously, or component (b) is added at first and component (c) is added while the mixture is being blended, or component (c) is added at first and then component (b) is added while the mixture is being blended. Finally, component (d) is added and blended; alternatively, component (a) is softened as described above, and components (b), (c) and (d) are all added simultaneously and the mixture is blended; alternatively, components (a), (b) and (c) are added simultaneously to the above-mentioned mixer or roll mill and the mixture is blended, then component (d) is added to the homogeneous mixture; alternatively, all components (a), (b), (c) and (d) are added simultaneously to the above-mentioned mixer or roll mill and the mixture is blended; alternatively, all of or a portion of additives such as fillers, plasticizers, softening agents, antioxidants, vulcanizing agents and vulcanization accelerators are added to the component (a) in advance and the other three components are then added to the mixture, and the mixture is blended; alternatively, a mixture of (a) containing all or a portion of additives such as fillers, plasticizers, softening agents, antioxidants, vulcanizing agents and vulcanization accelerators, component (b) containing additives such as reinforcing fillers such as fumed silica or wet process silica and heat resistance improving agents, and component (c) are blended in the above-mentioned mixer or roll mill, and then the component (d) is added to the mixture and the mixture is blended.
Thus, the method of addition, the order of addition, the method of blending, the conditions for blending and the apparatus for blending are not critical. However, if the mixture contains component (d) the heat of the mixture must be controlled during blending at a sufficiently low level such that component (d) is not decomposed.
The compounded rubber compositions are generally vulcanized at a temperature ranging from 80.degree. to 200.degree. C. for a few minutes to 3 hours, under a pressure of 20-200 kg/cm.sup.2. Secondary vulcanization or post cure can be carried out if needed, at a temperature ranging from 80.degree. to 180.degree. C. for 1 to 48 hours to obtain useful rubber products.
The vulcanized compounded rubber has excellent heat resistance compared to compounds without the addition of the component (c).
In the compounded rubber compositions of the present invention inadequate strength of silicone rubber is compensated by the natural rubber or synthetic rubber, while the inadequate heat resistance of natural rubber or synthetic rubber is compensated by the silicone rubber. Thus, the products can be serviceable in a wide range of applications requiring both strength and heat resistance.